US8367247B2 - Cathode active material for lithium secondary batteries with high safety, method of preparing the same and lithium secondary batteries comprising the same - Google Patents

Cathode active material for lithium secondary batteries with high safety, method of preparing the same and lithium secondary batteries comprising the same Download PDF

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US8367247B2
US8367247B2 US12/528,151 US52815108A US8367247B2 US 8367247 B2 US8367247 B2 US 8367247B2 US 52815108 A US52815108 A US 52815108A US 8367247 B2 US8367247 B2 US 8367247B2
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active material
cathode active
lithium
oxide
secondary battery
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US20100310940A1 (en
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Seong-Bae Kim
Woo-Seong Kim
Yoon-Jeong Heo
Sung-Tae Ko
Ji-Jun Hong
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SolarEdge Technologies Korea Co Ltd
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Kokam Ltd Co
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    • C01G45/1228—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof of the type [MnO2]n-, e.g. LiMnO2, Li[MxMn1-x]O2
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Definitions

  • the present invention relates to a cathode active material for lithium second batteries with high safety, a method for preparing the same, and a lithium secondary battery having the same. More particularly, the present invention relates to a cathode active material capable of improving safety of the cathode active material for a lithium ion secondary battery or a lithium ion polymer battery, particularly thermal stability and overcharging characteristics, and a method for preparing the same.
  • lithium secondary batteries are actively progressing not only in Korea but also in Japan, Europe and USA on lithium secondary batteries as an environment-friendly power source that may be applied to electric vehicles, uninterruptible power supplies, electromotive tools and satellites.
  • a spinel-type lithium manganese-based battery has ever been applied to cellular phones at one time.
  • its advantages such as low price and high safety are not utilized due to its gradually deteriorated energy density.
  • an olivine-type ferric phosphate lithium compound has very low electron conductivity in spite of advantages such as low price and high safety, so excellent battery characteristics are not expected. Also, an average operating potential of the olivine-type ferric phosphate lithium compound is low, which does not satisfy the demands on high capacity.
  • Japanese Laid-open Patent Publication No. 2001-143705 discloses a cathode active material in which a lithium cobalt oxide and a lithium manganese oxide are mixed.
  • this material is just obtained by simply mixing a lithium manganese oxide with excellent safety, so it does not improve characteristics sufficiently.
  • Japanese Laid-open Patent Publication No. 2002-143708 proposes a cathode active material in which lithium nickel composite compounds with different compositions are provided in two layers.
  • a cathode active material having two layers of lithium nickel composite compounds with different compositions is applied, it cannot be considered as fundamentally sufficiently improving the safety caused by overcharging.
  • Japanese Laid-open Patent Publication No. 2007-012441 discloses a cathode having two or more cathode active material layers to improve the overcharging characteristics, where an olivine-type ferric phosphoric lithium oxide or a spinel-type lithium manganese oxide is added to the layer contacting with a cathode current collector.
  • an olivine-type ferric phosphoric lithium oxide or a spinel-type lithium manganese oxide is added to the layer contacting with a cathode current collector.
  • oxide layers are formed with a thickness not greater than its average particle size, namely in a level of several micrometers, and conductive material or auxiliary conductive material is not included, so it cannot be considered as having sufficient high-current discharging characteristics.
  • Japanese Laid-open Patent Publication No. 2006-318815 discloses a technique for coating a surface of secondary particle with lithium salt or lithium oxide so as to improve durability of a lithium nickel oxide.
  • a dry-coating process and a wet-coating process should be added, the productivity is greatly deteriorated.
  • Japanese Laid-open Patent Publication No. 2006-19229 proposes to coat a surface of secondary particle with lithium cobalt zirconium oxide for the purpose of improving the safety of lithium nickel oxide with weak safety.
  • a dry-coating process should also be applied to coat the surface of lithium nickel oxide secondary particle with lithium cobalt zirconium oxide, the productivity is deteriorated though its effect is remarkably improved.
  • the present invention is designed to solve the problems of the prior art, and therefore it is an object of the present invention to provide a cathode active material capable of greatly improving safety, particularly thermal stability and overcharging characteristics, without deteriorating basic characteristics of the cathode active material itself, and to provide a method for preparing such a cathode active material with excellent productivity and reproduction.
  • the present invention provides a cathode active material for a lithium secondary battery, which includes a lithium metal oxide secondary particle core formed by agglomerating lithium metal oxide primary particles; and a shell formed by coating the secondary particle core with barium titanate and metal oxide.
  • the cathode active material for a lithium secondary battery according to the present invention may improve thermal stability while keeping excellent electric characteristics by coating a lithium metal oxide secondary particle with barium titanate and metal oxide.
  • Barium titanate changes its crystal structure at about 125° C. to greatly increase an electric resistance as mentioned above, thereby improving thermal stability of the cathode active material.
  • the sell made of the cathode active material according to the present invention may further include olivine-type ferric phosphate lithium oxide and/or conductive material, selectively. If overcharging occurs, the olivine-type ferric phosphate lithium oxide may limit discharge of lithium from lithium metal oxide corresponding to the core to improve the safety of the cathode active material against overcharging, and the conductive material may improve discharging characteristics of the cathode active material.
  • a method for preparing a cathode active material for a lithium secondary battery which includes (S 1 ) firing metal hydroxide and lithium salt to make a lithium metal oxide secondary particle core in which lithium metal oxide primary particles are agglomerated; (S 2 ) dry-coating the core with barium titanate and metal oxide to form a shell on an outer surface of the core; and (S 3 ) thermally treating the resultant material.
  • the method for preparing a cathode active material for a lithium secondary battery according to the present invention adopts the dry-coating process, so it allows coating the surface of cathode active material with barium titanate and metal oxide corresponding to the shell with excellent reproduction in an efficient way while keeping a conductive passive film existing on the surface of the cathode active material corresponding to the core.
  • the thermal treatment of the step (S 3 ) may be conducted at 300 to 600° C. for 4 to 12 hours.
  • the cathode active material for a lithium secondary battery may be used for making a cathode of a lithium secondary battery, or a lithium secondary battery having such a cathode.
  • FIG. 1 is a SEM (Scanning Electronic Microscope) photograph showing cathode active materials prepared according to a comparative example 1(a), a example 1(b) of the present invention, a comparative example 2(c) and an example 5(d) of the present invention;
  • FIG. 2 is a mapping SEM photograph showing a cathode active material particle prepared according to an example 5 of the present invention (a: mapping image, b: Ti mapping, c: Fe mapping, d: P mapping, and e: C mapping);
  • FIG. 3 is a graph showing an initial charging/discharging curve of cathode active materials prepared according to a comparative example 1 and an example 4 of the present invention
  • FIG. 4 is a graph showing an initial charging/discharging curve of cathode active materials prepared according to a comparative example 2 and an example 5 of the present invention
  • FIG. 5 is a graph showing a thermal stability characteristic according to hotbox storage of a pouch battery to which the cathode active material prepared according to the comparative example 1 is applied;
  • FIG. 6 is a graph showing a thermal stability characteristic according to hotbox storage of a pouch battery to which the cathode active material prepared according to the example 4 of the present invention is applied;
  • FIG. 7 is a graph showing overcharging characteristics of a pouch battery to which the cathode active material prepared according to the example 4 of the present invention is applied.
  • FIG. 8 is a graph showing behavior of a pouch battery to which the cathode active material prepared according to the example 4 of the present invention is applied, according to a nail penetration test.
  • FIG. 9 is a graph showing the results of a self-heating test on a pouch battery using the cathode active material prepared according to the example 4 of the present invention and on a pouch battery using the cathode active material of the comparative example 1.
  • metal hydroxide and lithium salt are fired to make a lithium metal oxide secondary particle core in which lithium metal oxide primary particles are agglomerated (S 1 ).
  • the lithium metal oxide available in the present invention may employ any lithium metal oxide used as a cathode active material of a lithium secondary battery in the art, with no limitation except olivine-type ferric phosphate lithium oxides.
  • the lithium metal oxide secondary particle used as a core in the present invention is configured such that lithium metal oxide primary particles are agglomerated therein, and it is made by firing metal hydroxide and lithium salt, as explained below in detail.
  • metal hydroxide employs various raw materials correspondingly according to a targeted cathode active material.
  • metal salt may use sulphate, nitrate, acetate or the like.
  • a solution containing such metal salt is successively put under the coprecipitation circumstance to successively take slurry containing metal hydroxide in the form of reactant, and then metal hydroxide is made by means of washing, filtration and drying.
  • metal hydroxide is used in making a lithium metal oxide as mentioned above, it is possible to restrict introduction of impurities contained in each metal salt, to control a composition to the atom level, to maximize an adding effect of different kinds of elements introduced with a small amount, and to easily make a lithium metal oxide having a uniform crystal structure with substantially no impurity.
  • the lithium metal oxide of the present invention may be made by thermally treating the metal hydroxide, prepared from raw material precursors by the hydroxide coprecipitation method, at a certain temperature and mixing it with various kinds of lithium salts into a desired composition, and then firing it under a common firing condition.
  • the lithium metal oxide prepared as mentioned above is obtained as a lithium metal oxide secondary particle in which lithium metal oxide primary particles are agglomerated.
  • An average diameter of the primary particles that configure the secondary particle may be variously changed depending on coprecipitation circumstances according to a composition ratio of the metal hydroxide, and it is not limited to any range.
  • an average diameter of the secondary particles may be variously changed depending on usage or production circumstances, and it may be 7 to 15 ⁇ m for example, but not limitedly.
  • the average diameter of the secondary particles is in the above range, the stability of secondary particles becomes more excellent in a following dry-coating process of barium titanate and metal oxide, and the efficiency and reproduction of the coating process are further improved.
  • the shape of the secondary particle is not specially limited, but the efficiency of the coating process for applying olivine-type ferric phosphate lithium oxide to a surface of the secondary particle may be further improved when the secondary particle has a spherical shape.
  • the core is dry-coated with barium titanate and metal oxide to form a shell on an outer surface of the core (S 2 ).
  • barium titanate used herein includes not only pure barium titanate but also barium titanate to which a small amount (0.1 to 1.5 weight %) of elements such as La, Ce, Nd, Pr, Sm, Gd, Nb, Bi, Sb and Ta are added.
  • Barium titanate is a high dielectric material, and it is a PTC (Positive Temperature Coefficient) thermistor whose resistance is increased as temperature increases.
  • the barium titanate changes its crystal structure at about 125° C. to greatly increase an electric resistance as mentioned above, so it may improve thermal stability of the cathode active material according to the present invention.
  • An average diameter of the barium titanate employed in the present invention may be changed variously according to usage and production circumstance, and for the purpose of the present invention, the average diameter is preferably not greater than 1 ⁇ m. As the average diameter is far smaller than 1 ⁇ m, the efficiency of the dry-coating process executed in the present invention may be maximized, so the average diameter has no lower limit. For example, the average diameter may be 1 nm, but not limitedly. If the average diameter exceeds 1 ⁇ l, the efficiency and reproduction of the surface-coating process of a metal composite oxide corresponding to the core are deteriorated, undesirably.
  • a material to be coated should have a sufficient specific surface area so as to coat the surface of the cathode active material, namely a specific surface area, into a film shape.
  • the average diameter exceeds 1 ⁇ l, the ratio of material participating in the coating process is decreased, and the material partially remains as a simple mixture, undesirably.
  • the content of barium titanate employed in the present invention may be suitably selected according to the kind of battery using the cathode active material.
  • the content of barium titanate may be 0.05 to 1 parts by weight, based on 100 parts by weight of the core, but not limitedly. If the content is less than 0.05 parts by weight, the effect of barium titanate is insufficient. If the content exceeds 1 part by weight, as the content is increased, the high-rate characteristics may be deteriorated due to the deterioration of specific capacity and the reduction of conductivity of the cathode active material.
  • the metal oxide having a nanometer size plays a role of binder between the barium titanate and the core, and it gives a direct influence on disintegration or spherization of the core. Also, the metal oxide prevents direct contact of electrolyte to the core, thereby further improving stability and cycle characteristics. In addition, various additional improvements in properties may be made according to the kind of metal oxide.
  • lithium metal oxide may be further included, from which improvement in rapid charging/discharging characteristics and cycle characteristics is expected without decreasing a battery capacity.
  • the lithium metal oxide may use a layered lithium metal composite oxide, a lithium cobalt oxide, a spinel-type lithium manganese oxide and so on.
  • the coating material applied to the shell is not limited to the above, but various kinds of nano-size metal oxide materials may be used in combination according to desired improvement in functionality of the shell such as stability, high temperature characteristics and conductivity.
  • the average diameter of the metal oxide employed in the present invention may be variously changed according to usage and production circumstance, for example 1 to 100 nm, but not limitedly. In the above range of average diameter, it is possible to control the reduction of a battery capacity to the minimum and thus maximize the effect of a formed shell. In detail, as the average diameter is smaller, the specific surface area participating in coating is maximized, so the shell may be formed with only a small amount of metal oxide and thus its effect may be maximized. If the metal oxide has a size less than 1 nm, it is not easy to prepare the material itself, so the cost for producing the core-shell type cathode active material may be increased. If the metal oxide has a size exceeding 100 nm, the specific surface area is decreased, so an amount of metal oxide is increased to coat the shell into a film shape, which may decrease a battery capacity.
  • the content of metal oxide employed in the present invention may be suitably selected according to the kind of battery using the cathode active material.
  • the content of metal oxide may be 0.05 to 1 parts by weight, based on 100 parts by weight of the core, but not limitedly. If the content is less than 0.05 parts by weight, the effect of metal oxide is insufficient. If the content exceeds 1 part by weight, a specific capacity of cathode active material may be deteriorated.
  • an olivine-type ferric phosphate lithium oxide having the greatest increase rate of resistance according to overcharging may be included in the shell-forming material, and then it may be applied to the core.
  • the olivine-type ferric phosphate lithium oxide limits the contact between the cathode active material of the core and the electrolyte at overcharging. Accordingly, an amount of lithium discharged from the cathode active material of the core is limited, and thus an amount of lithium precipitated on the anode is reduced, which decreases a caloric value caused by the reaction with electrolyte, thereby improving safety, particularly against overcharging.
  • An average diameter of the olivine-type ferric phosphate lithium oxide employed in the present invention may be changed variously according to usage and production circumstance, and for the purpose of the present invention, the average diameter is preferably not greater than 1 ⁇ m. As the average diameter is far smaller than 1 ⁇ m, the efficiency of the dry-coating process executed in the present invention may be maximized, so the average diameter has no lower limit. For example, the average diameter may be 1 nm, but not limitedly. If the average diameter exceeds 1 ⁇ m, the efficiency and reproduction of the surface-coating process of a metal composite oxide corresponding to the core are deteriorated, undesirably.
  • the content of olivine-type ferric phosphate lithium oxide employed in the present invention may be suitably selected according to the kind of battery using the cathode active material.
  • the content of olivine-type ferric phosphate lithium oxide may be 0.05 to 5 parts by weight, based on 100 parts by weight of the core, but not limitedly. If the content is less than 0.05 parts by weight, the purpose of applying the olivine-type ferric phosphate lithium oxide, namely the purpose for improving overcharging characteristics, is not sufficiently accomplished. If the content exceeds 5 part by weight, an amount of olivine-type ferric phosphate lithium oxide not participating in the coating process but existing as a simple mixture is increased, which may give bad influences such as deterioration of average discharge voltage, undesirably.
  • a conductive material may be included in the shell-forming material and then applied to the core.
  • the conductive material controls the increase of powder resistance caused by the shell-forming material, thereby allowing the cathode active material to keep excellent discharging characteristics.
  • the conductive material employed in the present invention may include conductive metal, conductive polymer and conductive carbon, Ketjen black, acetylene black, Super-P, graphite, activated carbon and so on as examples of the conductive carbons, however the present invention is not limited thereto.
  • the conductive material preferably has an average particle size of 1 ⁇ m all or less. As the average particle size is smaller than 1 ⁇ m, a specific surface area of the conductive material increases to reduce its addition amount, so the minimum of the average particle size is not limited to a specific value.
  • a conductive material may have an average particle size of 1 nm, but not limitedly. If the average particle size exceeds 1 ⁇ m, it is difficult to form a shell together with other shell-forming materials due to the great size, undesirably.
  • the content of the conductive material included in the shell according to the present invention may be suitably selected according to the kind of battery using the cathode active material. For example, 0.1 parts or more by weight of the conductive material may be included based on 100 parts by weight of the core, but the present invention is not limited thereto. If the content of the conductive material is less than 0.1 parts by weight, the used conductive material gives insignificant effect. Also, in the case that an excessive amount of conductive material is used, surplus conductive material remains on the surface of the cathode active material of the core, and it eliminates the need of an additional conductive material while preparing slurry, thereby reducing the time required to prepare the slurry.
  • the content of the conductive material in the shell is preferably not greater than 10 parts by weight, more preferably not greater than 5 parts by weight, most preferably not greater than 3 parts by weight, but not limitedly.
  • the dry-coating method used in the present invention is executed such that a coating material corresponding to the shell is applied to a surface of a cathode active material corresponding to the core in a mechanical way, which may gives a shearing force, a collision force or a compression force according to a used equipment, so this method allows simple blending as well as coating.
  • a cathode active material obtained by firing lithium and metal hydroxide as a raw material precursor at a high temperature necessarily requires pulverization and classification since sintering happens by some hydroxide precursors with bad spherical shape or an excessive amount of lithium.
  • the lithium metal oxide corresponding to the shell and/or the carbonaceous material of the core are made into spherical shape and disintegrated at the same time by the nanometer-size metal oxide corresponding to the shell, so the powder characteristics may be improved.
  • the resultant material is thermally treated (S 3 ).
  • the thermal treatment conditions can be suitably selected according to production circumstances such as the kind of cathode active material of the core.
  • the thermal treatment may be conducted at 300 to 600° C. for 4 to 12 hours, but not limitedly.
  • the shell exhibits very excellent density, the crystal structure defect of the core may be sufficiently compensated, and the structure of the core may be stably maintained.
  • the thermal treatment time ensures sufficient effects in the above range. If the thermal temperature time exceeds 12 hours, there is expected no additional effects though the thermal treatment time is increased further.
  • the cathode active material for a lithium secondary battery prepared according to the present invention may be adhered to at least one surface of a cathode electric collector using a binder resin to form a cathode of a lithium secondary battery.
  • the binder resin and the cathode current collector may adopt any common one used in the art without any limitation.
  • the cathode for a lithium secondary battery according to the present invention may be used for making a lithium secondary battery together with an anode, a separator interposed between the cathode and the anode, and an electrolyte.
  • the anode, the separator and the electrolyte may adopt any common one used in the art without any limitation.
  • Nickel sulfate (NiSO 4 .6H 2 O), manganese sulfate (MnSO 4 .H 2 O) and cobalt sulfate (CoSO 4 .7H 2 O) were dissolved in a refined ion exchange water such that nickel, cobalt and manganese had a mole ratio of 0.5:0.2:0.3, thereby making a metal solution. Also, a sodium hydroxide and an ammonia solution were prepared.
  • a coprecipitation reactor was used in pH 11.2 and 400 rpm to supply the metal solution at a rate of 5 L/hr and the ammonia solution at a rate of 0.5 L/hr under an inert nitrogen circumstance by means of a quantitative pump.
  • the sodium hydroxide solution was intermittently put such that the solution in the reactor could keep 11.2 pH constantly.
  • the reaction was executed over 48 hours to obtain slurry containing metal composite hydroxide of regular size.
  • a centrifugal separator-type filter was used to wash and filter the slurry until a filtered solution had pH 9.0 or below, and then the obtained metal composite hydroxide powder was dried at 120° C. over 24 hours to make metal composite hydroxide.
  • the metal composite hydroxide was thermally treated over 12 hours at a temperature of 300° C., and then it was mixed with lithium salt such that a stoichiometric ratio with lithium salt becomes 1:1.1.
  • This mixture was fired for 24 hours at 950° C. in a high temperature firing furnace capable of controlling temperature, and for 24 hours at 500° C.
  • pulverization and classification were conducted to make a metal composite oxide with a controlled average diameter, and then it was thermally treated for 4 hours at 500° C.
  • the made metal composite oxide had a ratio of Ni:Co:Mn as 0.50:0.20:0.30 and had an average diameter D 50 of 9.7 ⁇ m.
  • the above results are listed in brief in the tables 1 and 2, presented below.
  • the obtained metal composite oxide was used as a core, and barium titanate having an average diameter D 50 of 220 nm and titanium oxide having an average diameter D 50 of 20 nm were used as coating materials to make a core-shell type cathode active material.
  • a dry-coating equipment (NOB-130, produced by Hosogawa Micron Co. Ltd., Japan) was applied to mix 6 g of barium titanate and 0.6 g of titanium oxide respectively to 600 g of metal composite oxide such that weight ratios of barium titanate corresponding to a shell and titanium oxide to 100 parts by weight of the core are respectively 1 part by weight and 0.1 part by weight. After that, the mixture was processed at 2700 rpm for 3 minutes and then thermally treated at 500° C. for 4 hours, thereby making a core-shell type cathode active material.
  • a cathode active material was made in the same way as the example 1, except that the content of barium titanate was set to 0.2 parts by weight, based on 100 parts by weight of the core.
  • a cathode active material was made in the same way as the example 1, except that 1.5 parts by weight of olivine-type ferric phosphate lithium oxide having an average diameter D 50 of 150 nm was further added based on 100 parts by weight of the core in addition to the barium titanate and the titanium oxide, which configure the shell.
  • a cathode active material was made in the same way as the example 3, except that 0.2 parts by weight of Super P having an average diameter D 50 of 500 nm was further added based on 100 parts by weight of the core in addition to the barium titanate, the titanium oxide and the olivine-type ferric phosphate lithium oxide, which configure the shell.
  • a cathode active material was made in the same way as the example 4, except that the metal composite oxide was made to have a composition in which a ratio of Ni:Co:Mn is 0.40:0.30:0.30.
  • the metal composite oxide cores obtained in the examples 1 and 5 were respectively used as cathode active materials of the comparative examples 1 and 2.
  • Cathode active material, barium titanate, metal oxide, olivine-type ferric phosphate lithium oxide and Super-P used to form the core and the shell of the example 4 were simply mixed at the same ratio to make a cathode active material.
  • Average diameter and tap density of the cathode active materials prepared according to the examples 1 to 5 were measured before coating and after coating. The measurement results are listed in the following table 1. The average diameter was measured using a particle size distribution measurer (Mastersizer 2000E, produced by Malvern). While dispersing the cathode active material using ultrasonic wave, the average diameter D 50 was obtained by means of laser scattering. The tap density was measured from a volume change before and after 500 strokes were conducted, using 100 ml measuring cylinder.
  • Example 1 9.70 2.53 B, T 9.45 2.63
  • Example 2 9.70 2.53 B, T 9.52 2.61
  • Example 3 9.70 2.53 P, B, T 9.50 2.59
  • Example 4 9.70 2.53 P, B, T, C 9.54 2.57
  • Example 5 10.21 2.55 P, B, T, C 10.02 2.74
  • Comparative example 1 cathode active material of the example 1 before coating
  • FIG. 2 shows a sectional shape of the core-shell type cathode active material prepared according to the example 5 and a mapping image of each component (a: mapping image, b: Ti mapping, c: Fe mapping, d: P mapping, and e: C mapping).
  • the cathode active particle of the present invention exhibits excellent surface shape. Also, it was found that the coating material configuring the shell was also uniformly applied.
  • the cathode active material was mixed with a NMP solution obtained by melting Teflonized acetylene black as conductive material and PVDF as a binding agent to make slurry.
  • a mass ratio of the cathode active material, the conductive material and the binding agent was set to 90:3:7. This slurry was applied onto a 30 ⁇ m Al electric collector and then dried, and then it was compressed to a predetermined thickness and blanked into a diameter of 13 mm, thereby making a cathode.
  • the obtained cathode was used together with a lithium foil as an anode using a separator with a thickness of 20 ⁇ m to make a 2032 standard coin-type battery.
  • the electrolyte adopts 1.2 mol of LiPF 6 solution of a mixed solvent of ethylene carbonate and diethyl carbonate (at a volume ratio of 1:3).
  • Charge/discharge capacity of the battery was measured with a current density of 0.2 C at 25° C. in 2.5 ⁇ 4.2V voltage range using a charge/discharge cycle device, in which charge was measured under the constant current-constant voltage condition (0.02 C at a final charge stage) and discharge was measured under a constant current condition.
  • the measurement results are shown in the following table 2.
  • initial charge/discharge curves of the examples 4 and 5 and the comparative examples 1 and 2 are respectively shown in FIGS. 3 and 4 .
  • the specific capacity per unit mass and the initial efficiency of the cathode active materials were decreased according to the coating.
  • the specific capacity per unit mass of the cathode active material was decreased to some extend, but additional effects of each components of the shell were obtained.
  • the olivine-type ferric phosphate lithium oxide exhibits a stability improving effect against overcharging
  • the barium titanate exhibits a thermal stability improving effect against the exposure to high temperature
  • the titanium oxide exhibits a powder characteristic improving effect during a coating process and a binder effect for the coating materials of the shell.
  • the shell-forming material is simply mixed with lithium metal oxide of the core as in the comparative example 3, the shell-forming material just exists as impurities to the material corresponding to the core, so the initial capacity and the specific capacity were decreased.
  • the prepared cathode active material was mixed with an NMP solution obtained by dissolving carbon as conductive material and PVDF as a binding agent to make slurry.
  • NMP solution obtained by dissolving carbon as conductive material and PVDF as a binding agent
  • a mass ratio of the cathode active material, the conductive material and the binding agent was set to 92:4:4.
  • Graphite was used as an anode, and the cathode and the anode were placed to face each other with a separator being interposed between them.
  • the battery had a size of 3.7 mm in thickness, 64 mm in width and 95 mm in length, and a design capacity was set to 2000 mAh.
  • the battery was initially charged/discharged with a current density of 0.2 C (400 mAh) at 25° C. in 3.0 ⁇ 4.2V voltage range using a charge/discharge cycle device, and then charge/discharge experiments were conducted at various current densities.
  • the high rate characteristics was evaluated from a ratio of discharge capacity at 20 C current density using discharge capacity at 0.5 C current density as a criterion capacity.
  • the following table 3 shows high rate characteristics of the cathode active material obtained in the examples and the comparative examples.
  • FIGS. 5 and 6 shows hotbox storage characteristics of the example 1 and the comparative example 1.
  • the cathode active material for a lithium secondary battery according to the present invention includes a lithium metal oxide core and a shell coated with barium titanate and metal oxide, thereby improving safety of the lithium secondary battery, particularly thermal stability and overcharging characteristics.
  • the method for preparing a cathode active material for a lithium secondary battery according to the present invention ensures excellent reproduction and productivity in making a core-shell type cathode active material of the present invention.

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US10873089B2 (en) * 2017-12-12 2020-12-22 Toyota Jidosha Kabushiki Kaisha Positive electrode material and lithium secondary battery using the same
US11955631B2 (en) 2018-10-04 2024-04-09 Samsung Electronics Co., Ltd. Composite cathode active material, cathode and lithium battery each containing composite cathode active material, and method of preparing composite cathode active material

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WO2011068391A2 (ko) * 2009-12-04 2011-06-09 주식회사 루트제이제이 나노 중공 섬유형 탄소를 포함하는 리튬 이차전지용 양극 활물질 전구체, 활물질 및 그 제조방법
CN102918686B (zh) * 2010-06-02 2015-08-12 株式会社半导体能源研究所 电力储存装置
KR101256641B1 (ko) * 2010-11-02 2013-04-18 삼성에스디아이 주식회사 리튬 이차전지용 양극 활물질 및 이의 제조방법
KR101350811B1 (ko) 2010-11-17 2014-01-14 한양대학교 산학협력단 리튬 이차 전지용 양극 활물질, 이의 제조 방법 및 이를 포함하는 리튬 이차 전지
WO2012067449A2 (ko) * 2010-11-17 2012-05-24 한양대학교 산학협력단 리튬 이차 전지용 양극 활물질, 이의 제조 방법 및 이를 포함하는 리튬 이차 전지
JP5556797B2 (ja) * 2010-12-17 2014-07-23 トヨタ自動車株式会社 二次電池
KR101308677B1 (ko) * 2011-05-31 2013-09-13 주식회사 코캄 리튬 이차전지
US10044035B2 (en) * 2011-06-17 2018-08-07 Umicore Lithium cobalt oxide based compounds with a cubic secondary phase
JP5825006B2 (ja) * 2011-09-22 2015-12-02 藤倉化成株式会社 リチウムイオン二次電池用正極材、およびリチウムイオン二次電池
CN102394290A (zh) * 2011-11-18 2012-03-28 青岛华冠恒远锂电科技有限公司 一种锂离子电池正极材料及其制备方法
KR101465490B1 (ko) * 2011-11-30 2014-11-26 주식회사 코캄 안전성과 안정성이 향상된 리튬 이차 전지
US8604427B2 (en) * 2012-02-02 2013-12-10 Applied Materials Israel, Ltd. Three-dimensional mapping using scanning electron microscope images
KR20130109785A (ko) * 2012-03-28 2013-10-08 삼성에스디아이 주식회사 복합전극활물질, 이를 채용한 전극과 리튬전지 및 그 제조방법
JPWO2013154142A1 (ja) * 2012-04-11 2015-12-17 旭硝子株式会社 リチウムイオン二次電池用正極活物質
RU2554940C2 (ru) * 2012-04-25 2015-07-10 Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Московский государственный университет имени М.В. Ломоносова" (МГУ) Способ получения гибридного материала (варианты) для перезаряжаемых химических источников тока
KR101510179B1 (ko) * 2012-04-26 2015-04-08 주식회사 포스코이에스엠 리튬 망간 복합 산화물의 제조 방법, 그 제조 방법에 의하여 제조된 리튬 망간 복합 산화물, 및 이를 포함하는 리튬 이온 이차 전지
JP6008610B2 (ja) * 2012-06-27 2016-10-19 日揮触媒化成株式会社 二次電池用正極材および該正極材を用いた二次電池
KR101718058B1 (ko) 2012-08-01 2017-03-20 삼성에스디아이 주식회사 음극 활물질, 그 제조방법, 및 이를 채용한 리튬 전지
KR101439638B1 (ko) * 2012-11-06 2014-09-11 삼성정밀화학 주식회사 양극 활물질, 이의 제조방법 및 이를 포함하는 리튬 이차 전지
JP2014116296A (ja) * 2012-11-13 2014-06-26 Jgc Catalysts & Chemicals Ltd リチウム複合酸化物およびその製造方法、そのリチウム複合酸化物を含む二次電池用正極活物質、それを含む二次電池用正極、ならびにそれを正極として用いるリチウムイオン二次電池
KR101615413B1 (ko) * 2012-11-30 2016-04-25 주식회사 엘지화학 리튬 이차 전지용 양극, 이의 제조방법, 및 이를 포함하는 리튬 이차 전지
US9859550B2 (en) * 2012-12-14 2018-01-02 Umicore Lithium metal oxide particles coated with a mixture of the elements of the core material and one or more metal oxides
CN110510674B (zh) * 2013-03-15 2022-09-09 株式会社东芝 电池用电极材料及电池用基板、蓄电池、色素增感太阳能电池、电容器、Li离子二次电池
JP6352421B2 (ja) * 2013-09-02 2018-07-04 エルジー・ケム・リミテッド 二次電池用正極及びそれを含む二次電池
CN103441255B (zh) * 2013-09-16 2017-02-01 宁德新能源科技有限公司 锂离子电池正极材料及其制备方法
JP6371508B2 (ja) * 2013-09-25 2018-08-08 住友化学株式会社 リチウムイオン二次電池用正極活物質とその製造方法、リチウムイオン二次電池用正極、およびリチウムイオン二次電池
CN105813981A (zh) * 2013-12-17 2016-07-27 陶氏环球技术有限责任公司 改进的锂金属氧化物阴极材料及其制备方法
CN103825021B (zh) * 2014-03-12 2016-02-17 石哲文 一种稀土元素掺杂的复合钴酸锂正极材料的制备方法
KR102273772B1 (ko) 2014-05-21 2021-07-06 삼성에스디아이 주식회사 복합 양극 활물질, 이를 포함하는 리튬 전지, 및 이의 제조방법
US10141566B2 (en) * 2014-08-15 2018-11-27 Samsung Electronics Co., Ltd. Lithium secondary battery including a coated cathode material and solid electrolyte, and method of preparing the same
CN104810507A (zh) * 2014-09-02 2015-07-29 万向A一二三系统有限公司 一种锂离子软包电池正极浆料、其制备方法及其应用
CN104218234B (zh) * 2014-09-11 2017-11-17 浙江美达瑞新材料科技有限公司 一种高循环性能的锂离子电池复合正极材料及其制备方法
JP6137217B2 (ja) * 2015-02-12 2017-05-31 トヨタ自動車株式会社 非水電解質二次電池用負極の製造方法
CN105006574A (zh) * 2015-06-13 2015-10-28 浙江美达瑞新材料科技有限公司 一种表面改性的锂离子电池正极材料及其制备方法
CN105098161A (zh) * 2015-09-08 2015-11-25 湖南杉杉新材料有限公司 一种锂离子电池镍基多元正极材料及其制备方法
KR101982790B1 (ko) * 2015-10-20 2019-05-27 주식회사 엘지화학 다층 구조의 리튬 금속 산화물들을 포함하는 리튬 이차전지용 양극 활물질 및 그것을 포함하는 양극
JP6304198B2 (ja) * 2015-11-04 2018-04-04 トヨタ自動車株式会社 非水電解液二次電池および非水電解液二次電池の製造方法
WO2017106168A1 (en) * 2015-12-14 2017-06-22 Massachusetts Institute Of Technology Solid oxygen-redox nanocomposite materials
TWI633692B (zh) * 2016-03-31 2018-08-21 烏明克公司 供汽車應用的鋰離子電池組
US20180070633A1 (en) * 2016-09-09 2018-03-15 Rai Strategic Holdings, Inc. Power source for an aerosol delivery device
KR102006726B1 (ko) 2016-10-05 2019-08-02 주식회사 엘지화학 이차전지용 양극활물질 및 이를 포함하는 이차전지
US10665849B2 (en) 2017-03-20 2020-05-26 The Boeing Company Battery cell design for preventing internal short circuits from occurring and propagating
US10651514B2 (en) * 2017-03-20 2020-05-12 The Boeing Company Battery cell design for preventing internal short circuits from occurring and propagating using positive temperature coefficient (PTC) materials
WO2018220972A1 (ja) * 2017-05-29 2018-12-06 太平洋セメント株式会社 リチウムイオン二次電池用正極活物質複合体及びこれを用いた二次電池、並びにリチウムイオン二次電池用正極活物質複合体の製造方法
JP7056659B2 (ja) * 2017-06-28 2022-04-19 住友金属鉱山株式会社 非水電解質二次電池用正極活物質、およびその製造方法、並びに、非水電解質二次電池
JP7031150B2 (ja) * 2017-07-05 2022-03-08 住友金属鉱山株式会社 非水系電解質二次電池用正極活物質、非水系電解質二次電池用正極活物質の製造方法、および該正極活物質を用いた非水系電解質二次電池
KR102174720B1 (ko) * 2017-11-23 2020-11-05 주식회사 에코프로비엠 리튬복합산화물 및 이의 제조 방법
JP6791112B2 (ja) * 2017-12-25 2020-11-25 日亜化学工業株式会社 非水系二次電池用正極材料の製造方法
WO2019166253A1 (en) * 2018-02-28 2019-09-06 Basf Se Process for making a coated electrode active material
CN112204775A (zh) * 2018-05-21 2021-01-08 微宏动力系统（湖州）有限公司 制备颗粒前体和阴极活性颗粒的方法及其制备的颗粒前体
EP3804008A4 (en) * 2018-06-11 2022-03-30 Microvast Power Systems Co., Ltd. METHODS FOR PREPARING PARTICLE PRECURSORS AND PARTICLE PRECURSOR PREPARED THEREOF
CN109192961B (zh) * 2018-09-20 2020-11-06 昶联金属材料应用制品(广州)有限公司 正极材料的制备方法
JP7085135B2 (ja) * 2018-10-12 2022-06-16 トヨタ自動車株式会社 正極活物質および該正極活物質を備える二次電池
JP7111638B2 (ja) * 2019-02-21 2022-08-02 トヨタ自動車株式会社 リチウム二次電池の正極材料
GB201913817D0 (en) * 2019-09-25 2019-11-06 Johnson Matthey Plc Process
EP4060759A4 (en) * 2019-11-15 2023-12-06 Vehicle Energy Japan Inc. POSITIVE ELECTRODE FOR LITHIUM-ION SECONDARY BATTERIES, AND LITHIUM-ION SECONDARY BATTERY
KR102633758B1 (ko) * 2020-06-01 2024-02-05 삼성에스디아이 주식회사 복합양극활물질, 이를 채용한 양극과 리튬전지 및 그 제조방법
KR102633759B1 (ko) * 2020-06-01 2024-02-05 삼성에스디아이 주식회사 복합양극활물질, 이를 채용한 양극과 리튬전지 및 그 제조방법
CN111653752B (zh) * 2020-06-24 2021-11-09 蜂巢能源科技有限公司 一种正极材料、其制备方法和锂离子电池
CN112583071B (zh) * 2020-11-27 2022-08-02 上海航天控制技术研究所 一种深空探测分离监视伴星的供电系统
DE102020132661A1 (de) 2020-12-08 2022-06-09 Bayerische Motoren Werke Aktiengesellschaft Kathodenaktivmaterial und Lithiumionen-Batterie mit dem Kathodenaktivmaterial
KR20230078382A (ko) * 2021-11-26 2023-06-02 삼성에스디아이 주식회사 복합양극활물질, 이를 채용한 양극과 리튬전지 및 그 제조방법

Citations (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20000061755A (ko) 1999-03-30 2000-10-25 김순택 리튬 이차 전지용 양극 활물질 및 그 제조 방법
KR100277796B1 (ko) 1998-02-10 2001-02-01 김순택 리튬 이차 전지용 양극 활물질 및 그 제조 방법
JP2001143705A (ja) 1999-11-12 2001-05-25 Sanyo Electric Co Ltd 非水電解質二次電池
JP2002060225A (ja) 2000-08-18 2002-02-26 Ishihara Sangyo Kaisha Ltd コバルト酸リチウム凝集体、コバルト酸化物凝集体及びそれらの製造方法並びに該コバルト酸リチウム凝集体を用いてなるリチウム電池
KR20020024521A (ko) 2000-09-25 2002-03-30 김순택 리튬 이차 전지용 양극 활물질 및 그 제조 방법
JP2002143708A (ja) 2000-11-04 2002-05-21 Horin Kankei Tokuso:Kk 木材破砕機用破砕ドラム
US6727021B1 (en) * 1997-12-25 2004-04-27 Mitsubishi Denki Kabushiki Kaisha Lithium ion secondary battery
US20040258836A1 (en) 2003-06-23 2004-12-23 Besenhard Jurgen Otto Method for the synthesis of surface-modified materials
JP2006019229A (ja) 2004-07-05 2006-01-19 Kureha Corp リチウム二次電池用正極材およびその製造方法
JP2006179432A (ja) * 2004-12-24 2006-07-06 Hitachi Maxell Ltd 非水電解液二次電池
JP2006318815A (ja) 2005-05-13 2006-11-24 Nissan Motor Co Ltd 非水電解リチウムイオン電池用正極材料、これを用いた電池および非水電解リチウムイオン電池用正極材料の製造方法
US20070003829A1 (en) 2005-06-30 2007-01-04 Naoki Imachi Non-aqueous electrolyte battery and method of manufacturing the same
KR20070081831A (ko) * 2006-02-14 2007-08-20 주식회사 엘지화학 분산성이 향상된 나노입자 함유 전극활물질의 제조방법
EP1876664A1 (en) 2005-04-28 2008-01-09 Nissan Motor Co., Ltd. Positive electrode material for lithium ion battery with nonaqueous electrolyte, and battery using the same
JP2009176597A (ja) 2008-01-25 2009-08-06 Panasonic Corp 非水電解質二次電池
US7611804B2 (en) * 2004-03-31 2009-11-03 Hitachi Maxell, Ltd. Nonaqueous secondary battery and electronic equipment using the same
US7682740B2 (en) * 2004-02-07 2010-03-23 Lg Chem, Ltd. Organic/inorganic composite porous layer-coated electrode and electrochemical device comprising the same
US7923149B2 (en) * 2006-11-21 2011-04-12 Samsung Sdi Co., Ltd. Positive electrode for rechargeable lithium battery and rechargeable lithium battery including same

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3677975B2 (ja) * 1996-12-26 2005-08-03 三菱電機株式会社 電極及びこれを用いた電池
JP2001283861A (ja) * 2000-03-31 2001-10-12 Sony Corp 電池用電極及び非水電解質電池
US6753111B2 (en) * 2000-09-25 2004-06-22 Samsung Sdi Co., Ltd. Positive active material for rechargeable lithium batteries and method for preparing same
TWI251359B (en) * 2003-10-10 2006-03-11 Lg Cable Ltd Lithium secondary battery having PTC powder and manufacturing method thereof
US20080311479A1 (en) * 2005-12-06 2008-12-18 Lg Chem, Ltd. Electrode With Enhanced Safety and Electrochemical Device Having the Same
JP5088727B2 (ja) * 2006-03-17 2012-12-05 日本合成化学工業株式会社 リチウム二次電池
KR101147604B1 (ko) * 2007-10-12 2012-05-23 주식회사 엘지화학 젤리-롤형 전극조립체의 변형을 억제하기 위한 제조방법
KR100947181B1 (ko) * 2007-11-19 2010-03-15 주식회사 엘지화학 다공성 코팅층이 형성된 세퍼레이터 및 이를 구비한전기화학소자

Patent Citations (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6727021B1 (en) * 1997-12-25 2004-04-27 Mitsubishi Denki Kabushiki Kaisha Lithium ion secondary battery
KR100277796B1 (ko) 1998-02-10 2001-02-01 김순택 리튬 이차 전지용 양극 활물질 및 그 제조 방법
KR20000061755A (ko) 1999-03-30 2000-10-25 김순택 리튬 이차 전지용 양극 활물질 및 그 제조 방법
JP2001143705A (ja) 1999-11-12 2001-05-25 Sanyo Electric Co Ltd 非水電解質二次電池
JP2002060225A (ja) 2000-08-18 2002-02-26 Ishihara Sangyo Kaisha Ltd コバルト酸リチウム凝集体、コバルト酸化物凝集体及びそれらの製造方法並びに該コバルト酸リチウム凝集体を用いてなるリチウム電池
KR20020024521A (ko) 2000-09-25 2002-03-30 김순택 리튬 이차 전지용 양극 활물질 및 그 제조 방법
JP2002143708A (ja) 2000-11-04 2002-05-21 Horin Kankei Tokuso:Kk 木材破砕機用破砕ドラム
US20040258836A1 (en) 2003-06-23 2004-12-23 Besenhard Jurgen Otto Method for the synthesis of surface-modified materials
US7682740B2 (en) * 2004-02-07 2010-03-23 Lg Chem, Ltd. Organic/inorganic composite porous layer-coated electrode and electrochemical device comprising the same
US7611804B2 (en) * 2004-03-31 2009-11-03 Hitachi Maxell, Ltd. Nonaqueous secondary battery and electronic equipment using the same
JP2006019229A (ja) 2004-07-05 2006-01-19 Kureha Corp リチウム二次電池用正極材およびその製造方法
JP2006179432A (ja) * 2004-12-24 2006-07-06 Hitachi Maxell Ltd 非水電解液二次電池
EP1876664A1 (en) 2005-04-28 2008-01-09 Nissan Motor Co., Ltd. Positive electrode material for lithium ion battery with nonaqueous electrolyte, and battery using the same
JP2006318815A (ja) 2005-05-13 2006-11-24 Nissan Motor Co Ltd 非水電解リチウムイオン電池用正極材料、これを用いた電池および非水電解リチウムイオン電池用正極材料の製造方法
US20070003829A1 (en) 2005-06-30 2007-01-04 Naoki Imachi Non-aqueous electrolyte battery and method of manufacturing the same
JP2007012441A (ja) 2005-06-30 2007-01-18 Sanyo Electric Co Ltd 非水電解質電池及びその製造方法
KR20070081831A (ko) * 2006-02-14 2007-08-20 주식회사 엘지화학 분산성이 향상된 나노입자 함유 전극활물질의 제조방법
US7923149B2 (en) * 2006-11-21 2011-04-12 Samsung Sdi Co., Ltd. Positive electrode for rechargeable lithium battery and rechargeable lithium battery including same
JP2009176597A (ja) 2008-01-25 2009-08-06 Panasonic Corp 非水電解質二次電池

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10873089B2 (en) * 2017-12-12 2020-12-22 Toyota Jidosha Kabushiki Kaisha Positive electrode material and lithium secondary battery using the same
US11955631B2 (en) 2018-10-04 2024-04-09 Samsung Electronics Co., Ltd. Composite cathode active material, cathode and lithium battery each containing composite cathode active material, and method of preparing composite cathode active material

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